Phenyl trifluoroethylene



Patented Sept. 30, 1952 PHENYL TRIFLUOROETHYLENE Saul G. Cohen, Brighton, Mass., assignor to Polaroid Corporation, Cambridge, Mass, a corporation of Delaware,

No Drawing. Application April 16, 1949,' Serial No. 88,034 1 Thisinvention has for its object the preparation of a new composition of matter, phenyl trifluoroethylene,

or epfi-trifluorostyrene, and more particularly the preparation of such material in monomeric form as a useful polymerizable compound.

The composition of the present invention may be manufactured in the following manner:

1 Claim. (01. zest-s51) ethylbenzene, 12.5 g. (0.070 mole) of antimony trifluoride, and 0.56 g. (0.0035 mole) of bromine were. heated under reflux with stirring'for one hour :at 140 C. The product was taken up in ether, washed with 'dilute hydrochloric acid, sodium fluoride solution, aniline, hydrochloric acid, sodium bicarbonate and water, dried and distilled. There was obtained a forerun of 5.2 g. boiling from 66 to 92 C./38 mm., and three other fractions. The first of these, boiling from 9.2-94 C./38 mm. with a yield of 17.8 g. and an 12 1.4772, was mfi.} -trifiuoro-a,,8-dichloroethylbenzene,

78 g. (0.52 mole) of difiuorochloroacetyl chlor F F ride I o--cr ('31 n FCCCl was distilled over a period of three hours into a stirred suspension of 78 g. (0.59 mole) aluminum chloride in 46 g. (0.59 mole) benzene and 200 cc. carbon disulfide. The reaction was started at C. and the temperature was almost immediately reduced to 2-3 C., at which temperature the reaction was continued until the addition of the difiuorochloroacetyl chloride was completed. The reaction mixture was then brought to room temperature where it was maintained with continued stirring for one hour. The product was then decomposed in 600 g. of ice and 60 cc. of concentrated hydrochloric acid. The organic layer was separated, the aqueous layer was further extracted with ether, and the combined extracts were filtered, dried and dis- An analysis of the material obtained showed 30.3% chlorine as against a calculated quantity of 30.8%.

12.9 g. (0.056 mole) of a,B,fi-trifill010a,fi-di chloro-ethylbenzene, 3.8 g. (0.059 mole) of zinc dust, which had been washed several times with 1% hydrochloric acid and then with ethanol and. ether, and dried in vacuum, and a few crystals of dried zinc chloride in 15 cc. of absolute ethanol were boiled under reflux for two hours with occasional shaking. The product was decanted from residual solid (0.37 g.), diluted with ether, washed with 10% hydrochloric acid and water, dried and distilled. There was obtained 4.3 g. (48% yield) of a,fl,,8-trofluorostyrene or phenyl trifluoroethylene tilled, leading to difluorochloroacetophenone 0 F ccr i=+ r 67 g., 67% yield, B. P. 97 C./37 mm., n 1.4950.

76.5 g. of difluorochloroacetophenone (0.40 mole) and g. (0.60 mole) phosphorus pentahaving a boiling point of 68-70 C. at 75 mm., a melting point of 23 to -22 C., and an 22 1.4723. A sample was analyzed with the following result:

chloride were heated under reflux for 21 hours Amount ffga 2% 0% at a bath temperature of C. The reaction Amount found mixture was cooled to room temperature and 12.6

g. (0.21 mole) of acetone added. The mixture was warmed briefly and subjected to fractional distillation leading to 76.5 g. of B,p3-difluoro-a,a,5- trichloro-ethylbenzene,

There was thus obtained a new composition of matter, phenyl trifiuoroethylene in monomeric form, a water-clear, nonviscous liquid having a 11 F slight but inoffensive odor; a useful polymerizable 55 compound. u I I It is to be understood that the preferred meth- 78% yield, B. P. 98-99 C./15 mm., n 1.5103.

51 g. (0.21 mole) of pLp-difiuoro-a,a,p-trichloro- 0d of manufacturing the new composition of matter is not to be deemed to limit the invention. Other methods of manufacture may, if desired, be employed. For example, this material may be produced by the treatment of a,fl,1 fi,tetra- FF ll with zinc in alcohol, or the process which has here been described, in connection with the manufacture of the novel compound, --may be modified by employing ether instead of alcohol in connection with the reaction of the zinc and a,fi,p-trifluoro-a,,3-dichloro-ethylbenzene. Other modifications of the process may, if desired, be

" -It may perhaps be-wen wpoinu outi that 'the difiuorochloroac'etyl chloride: employed in zthe -initial' 's'tep of the ma'nu-facturing process= de -"scribed *may "preferably be;obtained by the -'reaction of sodium difluorochloroacetate and phosphorus oxychloride u'nder *refiugzljdlthough the material has also beenprepared by'the chlorination of difluoroethanol.

-file of 1 this patent:

UNITED STATES PATENTS Number Name Date 2,378,453 Weinmayer June 19, 1945 2,398,483 Weinmayer '.-Apr. .-1,2' 1946 OTHER REFERENCES McBee et a1., Industrial and Engineering Chem., V01. 39, p. 334-6 (194:7) 

